CN110499542B - Para-aramid fiber and preparation method thereof - Google Patents
Para-aramid fiber and preparation method thereof Download PDFInfo
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- CN110499542B CN110499542B CN201910924653.1A CN201910924653A CN110499542B CN 110499542 B CN110499542 B CN 110499542B CN 201910924653 A CN201910924653 A CN 201910924653A CN 110499542 B CN110499542 B CN 110499542B
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- 229920003235 aromatic polyamide Polymers 0.000 title claims abstract description 64
- 239000000835 fiber Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000000203 mixture Substances 0.000 claims abstract description 46
- 239000002994 raw material Substances 0.000 claims abstract description 40
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 21
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 20
- 239000000178 monomer Substances 0.000 claims abstract description 19
- WRDNCFQZLUCIRH-UHFFFAOYSA-N 4-(7-azabicyclo[2.2.1]hepta-1,3,5-triene-7-carbonyl)benzamide Chemical compound C1=CC(C(=O)N)=CC=C1C(=O)N1C2=CC=C1C=C2 WRDNCFQZLUCIRH-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000002798 polar solvent Substances 0.000 claims abstract description 18
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 17
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims abstract description 16
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 claims abstract description 16
- HEAHMJLHQCESBZ-UHFFFAOYSA-N 2,5-diaminobenzenesulfonic acid Chemical compound NC1=CC=C(N)C(S(O)(=O)=O)=C1 HEAHMJLHQCESBZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- MGLZGLAFFOMWPB-UHFFFAOYSA-N 2-chloro-1,4-phenylenediamine Chemical compound NC1=CC=C(N)C(Cl)=C1 MGLZGLAFFOMWPB-UHFFFAOYSA-N 0.000 claims abstract description 14
- ZBMISJGHVWNWTE-UHFFFAOYSA-N 3-(4-aminophenoxy)aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=CC(N)=C1 ZBMISJGHVWNWTE-UHFFFAOYSA-N 0.000 claims abstract description 14
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims abstract description 12
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000243 solution Substances 0.000 claims description 53
- 238000009987 spinning Methods 0.000 claims description 31
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 28
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 22
- 239000002904 solvent Substances 0.000 claims description 22
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 239000007864 aqueous solution Substances 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 18
- 238000005303 weighing Methods 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 12
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 11
- 229960001484 edetic acid Drugs 0.000 claims description 11
- 239000000945 filler Substances 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- 239000000843 powder Substances 0.000 claims description 9
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 239000004760 aramid Substances 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 230000005684 electric field Effects 0.000 claims description 6
- 230000009471 action Effects 0.000 claims description 5
- 239000002131 composite material Substances 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 4
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 4
- 238000005086 pumping Methods 0.000 claims description 4
- 238000005507 spraying Methods 0.000 claims description 4
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 4
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 3
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium oxide Inorganic materials O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 claims description 3
- 229910052588 hydroxylapatite Inorganic materials 0.000 claims description 3
- PVADDRMAFCOOPC-UHFFFAOYSA-N oxogermanium Chemical compound [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 claims description 3
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 claims description 3
- 235000010413 sodium alginate Nutrition 0.000 claims description 3
- 229940005550 sodium alginate Drugs 0.000 claims description 3
- 239000000661 sodium alginate Substances 0.000 claims description 3
- 229910052714 tellurium Inorganic materials 0.000 claims description 3
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims description 3
- OQMIRQSWHKCKNJ-UHFFFAOYSA-N 1,1-difluoroethene;1,1,2,3,3,3-hexafluoroprop-1-ene Chemical group FC(F)=C.FC(F)=C(F)C(F)(F)F OQMIRQSWHKCKNJ-UHFFFAOYSA-N 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 claims description 2
- 235000019982 sodium hexametaphosphate Nutrition 0.000 claims description 2
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 2
- 238000011068 loading method Methods 0.000 claims 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052744 lithium Inorganic materials 0.000 abstract description 5
- 239000002657 fibrous material Substances 0.000 abstract description 3
- 229920002994 synthetic fiber Polymers 0.000 abstract description 2
- 229920000642 polymer Polymers 0.000 description 23
- 238000006116 polymerization reaction Methods 0.000 description 13
- 239000000047 product Substances 0.000 description 11
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 10
- 229910001416 lithium ion Inorganic materials 0.000 description 10
- 229920003366 poly(p-phenylene terephthalamide) Polymers 0.000 description 10
- 230000008569 process Effects 0.000 description 10
- 229920006231 aramid fiber Polymers 0.000 description 6
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 5
- 238000007334 copolymerization reaction Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 238000002166 wet spinning Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000010668 complexation reaction Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000001523 electrospinning Methods 0.000 description 2
- 230000005686 electrostatic field Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000004005 microsphere Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- -1 poly phenylene terephthalamide Polymers 0.000 description 2
- 230000036632 reaction speed Effects 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 description 1
- 229920006293 Polyphenylene terephthalamide Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical group OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 238000000048 melt cooling Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920000889 poly(m-phenylene isophthalamide) Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000000935 solvent evaporation Methods 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
Images
Classifications
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/78—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products
- D01F6/80—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products from copolyamides
- D01F6/805—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products from copolyamides from aromatic copolyamides
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Polyamides (AREA)
Abstract
The invention relates to a para-aramid fiber and a preparation method thereof, and relates to the field of artificial fiber materials. The preparation method is a preparation method of para-aramid fiber, and is characterized in that para-phenylenediamine, o-chloro-para-phenylenediamine, 3,4' -diaminodiphenyl ether, 2, 5-diaminobenzene sulfonic acid and terephthaloyl chloride are used as monomer raw materials, a mixture of N, N-dimethylformamide, N-dimethylacetamide and N-methyl pyrrolidone is used as a polar solvent, poly-p-phenylene terephthalamide is prepared through low-temperature solution polycondensation, and the poly-p-phenylene terephthalamide is used for electrostatic spinning to prepare the para-aramid fiber. The para-aramid fiber obtained by the method has high solubility, good fluidity and stable electrochemical performance, and is particularly suitable for preparing a lithium battery diaphragm.
Description
Technical Field
The invention relates to the field of artificial fiber materials, in particular to para-aramid fiber and a preparation method thereof.
Background
Aramid fiber (poly phenylene terephthalamide) is an artificially synthesized fiber and has various excellent properties such as high strength, high modulus, high temperature resistance, acid and alkali resistance, light weight, insulation, aging resistance, long life cycle and the like, so that the aramid fiber is widely applied to various fields such as composite materials, bulletproof products, building materials, special protective clothing, electronic equipment and the like.
At present, the varieties with the most practical values in aramid fiber materials are two: the aramid fiber is meta-aramid fiber (PMIA) with zigzag molecular chain arrangement, which is called aramid fiber 1313 in China; the fiber is para-aramid fiber (PPTA) with linear molecular chain arrangement, which is called aramid 1414 in China.
Para-aramid is a typical-AA-BB-type polymer, intermolecular hydrogen bonds exist among amido bonds, a conjugated structure is formed between the amido bonds and a benzene ring, the internal rotation energy is quite high, and the para-aramid is characterized in that chain unit arrangement is regular, and the molecular crystallization and orientation degree is extremely high, so that a para-aramid macromolecular chain is in a coaxial or parallel rigid rod-shaped stretching structure. Due to the special molecular structure of the para-aramid, the para-aramid has the characteristics of high modulus, high strength, high heat resistance and the like, so that the para-aramid is widely applied to the aspects of the aerospace industry, the military industry, high-speed trains, cords, communication cables, sports goods and the like. In particular, para-aramid polymers have recently become a preferred new material for producing lithium ion battery separators due to their excellent physicochemical properties such as solvent resistance, heat resistance, and low thermal expansion coefficient.
However, due to the special linear rod-like structure of para-aramid, it cannot be dissolved in common organic solvents, and small molecular weight prepolymers precipitate from the solvent in the form of gel during polymerization. Therefore, the para-aramid fiber needs to be polymerized in a strong aprotic polar solvent such as NMP (N-methyl pyrrolidone), DMAC (N, N-dimethyl acetamide) or DMF (N, N-dimethyl formamide) during preparation. The characteristics cause great obstacles to the application of the para-aramid polymer in the field of lithium ion battery diaphragm manufacturing.
The low-temperature solution polycondensation method is a commonly used method for industrially synthesizing para-aramid at present, and adopts monomers with large activity, such as terephthaloyl chloride and p-phenylenediamine, as raw materials to carry out copolymerization in a nonpolar molecular solvent system under the condition of low temperature. The reaction requires small activation energy and high reactivity of reactants, so the reaction speed is very high, and the synthesis is carried out under low temperature conditions in order to control the reaction speed. At present, a low-temperature solution polycondensation process is generally carried out by adopting a batch type reaction kettle, a jacket is lined in a kettle body, different media can be introduced into the jacket, so that the reaction kettle is flexibly heated and cooled, and active groups can be protected by introducing compressed nitrogen.
In the technical field of producing para-aramid by a low-temperature solution polycondensation method, in order to reduce the crystallinity of a polymer and avoid phase change in the polymerization reaction process, a third monomer and even a fourth monomer are often required to be introduced to carry out copolymerization modification on the para-aramid polymer, so that the crystallinity of the polymer is reduced, and the fluidity and the solubility of the para-aramid polymer are improved. The currently widely used modification method is mainly to introduce other monomers to the main chain of para-aramid fiber for copolymerization with p-phenylenediamine and terephthaloyl chloride, so that the molecular chain is subjected to rigid bending or flexible distortion, the aggregation structure of the molecular chain is changed, the crystallinity of the polymer is reduced, and the solubility of the polymer is improved. For example, the invention patent with publication number CN107652430A discloses a production method of modified para-aramid polymer stock solution for positive and negative electrode separators of lithium ion batteries, which modifies the para-aramid polymer by changing or introducing a third monomer for copolymerization. On the premise of keeping the excellent physical and chemical properties of the para-aramid polymer, the modified para-aramid polymer has good fluidity and is beneficial to processing into a film. The diaphragm for the lithium ion battery, which is prepared from the modified para-aramid polymer, has the characteristics of high porosity, good heat-resistant shrinkage performance, high ionic conductivity and good electrochemical stability.
For spinning para-aramid, dry-jet wet spinning is generally adopted in the prior art. For example, the invention patent with the publication number of CN102154726A discloses a middle modulus poly-p-phenylene terephthamide fiber, which is prepared by using poly-p-phenylene terephthamide polymer with the logarithmic viscosity of 5.5-8.0dL/g obtained by adopting a low-temperature solution polycondensation method as a raw material and stretching wet yarn which is not dried in a dry-jet wet spinning process. The fiber product obtained by the method has the characteristics of high-crystallinity luster, bright color and less broken filaments.
However, the dry jet wet spinning process is only suitable for preparing para-aramid long fibers as textile materials. How to obtain disordered-arrangement para-aramid fibers which are specially suitable for preparing lithium ion battery separators and have excellent various performance parameters still remains a problem to be solved urgently for the field.
Disclosure of Invention
The invention provides the following technical scheme for solving the defects in the prior art.
A preparation method of para-aramid fiber is characterized by taking para-phenylenediamine, o-chloro-para-phenylenediamine, 3,4' -diaminodiphenyl ether, 2, 5-diaminobenzene sulfonic acid and terephthaloyl chloride as monomer raw materials, taking a mixture of N, N-dimethylformamide, N-dimethylacetamide and N-methyl pyrrolidone as a polar solvent, preparing poly (p-phenylene terephthalamide) through low-temperature solution polycondensation, and carrying out electrostatic spinning on the poly (p-phenylene terephthalamide) to prepare the para-aramid fiber.
Furthermore, 2 wt% -2.5 wt% of anhydrous lithium chloride is added into the polar solvent.
Further, the low-temperature solution polycondensation sequentially comprises primary polycondensation and secondary polycondensation; the primary polycondensation is carried out by taking p-phenylenediamine, o-chloro-p-phenylenediamine, 3,4' -diaminodiphenyl ether and 2, 5-diaminobenzene sulfonic acid as monomer raw materials at the temperature of 10-30 ℃; in the secondary solution polycondensation process, adding a terephthaloyl chloride monomer raw material into a first mixture obtained by the primary solution polycondensation, and carrying out secondary solution polycondensation at a temperature of-5 ℃ to 5 ℃.
Further, after poly-p-phenylene terephthamide is obtained through low-temperature solution polycondensation, the pH value is adjusted by using a sodium hydroxide aqueous solution, and the poly-p-phenylene terephthamide is washed by using an ethylene diamine tetraacetic acid aqueous solution and deionized water in sequence.
Further, in the electrostatic spinning process, a 50kV-80kV direct-current high-voltage electric field is applied to the spinning solution prepared by adopting the poly-p-phenylene terephthalamide.
Further, the preparation method of the para-aramid fiber comprises the following steps:
s1, respectively weighing p-phenylenediamine, o-chloro-p-phenylenediamine, 3,4' -diaminodiphenyl ether, 2, 5-diaminobenzenesulfonic acid and terephthaloyl chloride as monomer raw materials;
s2, respectively measuring N, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone as solvent raw materials, and adding anhydrous lithium chloride into the solvent raw materials to obtain a polar solvent;
s3, dissolving the p-phenylenediamine, the o-chloro-p-phenylenediamine, the 3,4' -diaminodiphenyl ether and the 2, 5-diaminobenzene sulfonic acid weighed in the step S1 in the polar solvent prepared in the step S2, and carrying out primary polycondensation under the protection of nitrogen and at the temperature of 10-30 ℃ to obtain a first mixture;
s4, adding the terephthaloyl chloride weighed in the step S1 into the first mixture obtained in the step S3, and carrying out secondary polycondensation under the conditions of nitrogen protection and the temperature of-5 ℃ to obtain a second mixture;
s5, adjusting the pH value of the second mixture obtained in the step S4 by using a sodium hydroxide aqueous solution, washing the second mixture by using an ethylene diamine tetraacetic acid aqueous solution and deionized water in sequence, and drying the second mixture to obtain poly (p-phenylene terephthalamide);
s6, preparing spinning solution from the poly-p-phenylene terephthalamide obtained in the step S5 by adopting tetrahydrofuran (THF is difficult to dissolve aramid resin, and amide (namely a solvent for polymerization) is generally adopted for dissolving);
and S7, preparing the spinning solution obtained in the step S6 into para-aramid fibers by adopting an electrostatic spinning device.
Further, the preparation method of the para-aramid fiber comprises the following steps:
s1, preparing p-phenylenediamine: o-chloro-p-phenylenediamine: 3,4' -diaminodiphenyl ether: 2, 5-diaminobenzenesulfonic acid: terephthaloyl chloride ═ (10-20): (10-20): (5-10): (5-10): (50-60) weighing monomer raw materials in a molar ratio;
s2, according to the weight ratio of N, N-dimethylformamide: n, N-dimethylacetamide: n-methylpyrrolidone ═ (20-30): (20-30): (40-60), weighing the solvent raw materials according to the volume ratio, uniformly mixing, and adding anhydrous lithium chloride: solvent raw materials (2-2.5): 100, adding anhydrous lithium chloride into the solvent raw material, heating to 80-100 ℃, and uniformly mixing again to obtain a polar solvent;
s3, adding the p-phenylenediamine, the o-chloro-p-phenylenediamine, the 3,4' -diaminodiphenyl ether and the 2, 5-diaminobenzenesulfonic acid weighed in the step S1 into a reaction kettle, pumping the polar solvent prepared in the step S2 into the reaction kettle, heating the mixture to 10-30 ℃ under the protection of nitrogen, and stirring the mixture until the mixture is completely dissolved to obtain a first mixture with the molar concentration of 0.4-0.5 mol/L;
s4, under the protection of nitrogen, cooling the first mixture obtained in the step S3 to-5 ℃ within 30min, adding the terephthaloyl chloride weighed in the step S1, and stirring for 10-30min until the reaction is finished to obtain a second mixture;
s5, adjusting the pH value of the second mixture obtained in the step S4 by using a 10 wt% -20 wt% sodium hydroxide aqueous solution, washing by using 0.02 wt% -0.04 wt% ethylene diamine tetraacetic acid aqueous solution and deionized water in sequence, and drying to obtain poly (p-phenylene terephthalamide);
s6, dissolving the poly-p-phenylene terephthalamide obtained in the step S5 in tetrahydrofuran, and uniformly mixing at the temperature of 40-60 ℃ to prepare 10-15 wt% of spinning solution;
s7, the spinning solution obtained in the step S6 is filled into an electrostatic spinning device, and is sprayed to form the para-aramid fiber under the action of a 50kV-80kV direct-current high-voltage electric field.
The para-aramid fiber is prepared by the preparation method.
The para-aramid fiber obtained by the method has high solubility, good fluidity and stable electrochemical performance, and is particularly suitable for preparing a lithium battery diaphragm.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings of the embodiments of the present invention will be briefly described below. Wherein the drawings are only for purposes of illustrating some embodiments of the invention and are not to be construed as limiting the invention to all embodiments thereof.
FIG. 1: the invention discloses a structural schematic diagram of an electrostatic spinning device.
Reference numerals: the device comprises an injector-1, a propeller-2, a capillary needle tube-3, a receiving device-4 and a high-voltage electricity generating device-5.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings of specific embodiments of the present invention. It should be noted that the technical features of the embodiments described in the present invention can be combined with each other without contradiction.
The invention provides a preparation method of para-aramid fiber, which specifically comprises the following steps:
s1, preparing p-phenylenediamine: o-chloro-p-phenylenediamine: 3,4' -diaminodiphenyl ether: 2, 5-diaminobenzenesulfonic acid: terephthaloyl chloride ═ (10-20): (10-20): (5-10): (5-10): (50-60) weighing monomer raw materials in a molar ratio;
s2, according to the weight ratio of N, N-dimethylformamide: n, N-dimethylacetamide: n-methylpyrrolidone ═ (20-30): (20-30): (40-60), weighing the solvent raw materials according to the volume ratio, uniformly mixing, and adding anhydrous lithium chloride: solvent raw materials (2-2.5): 100, adding anhydrous lithium chloride into the solvent raw material, heating to 80-100 ℃, and uniformly mixing again to obtain a polar solvent;
s3, adding the p-phenylenediamine, the o-chloro-p-phenylenediamine, the 3,4' -diaminodiphenyl ether and the 2, 5-diaminobenzenesulfonic acid weighed in the step S1 into a reaction kettle, pumping the polar solvent prepared in the step S2 into the reaction kettle, heating the mixture to 10-30 ℃ under the protection of nitrogen, and stirring the mixture until the mixture is completely dissolved to obtain a first mixture with the molar concentration of 0.4-0.5 mol/L;
s4, under the protection of nitrogen, cooling the first mixture obtained in the step S3 to-5 ℃ within 30min, adding the terephthaloyl chloride weighed in the step S1, and stirring for 10-30min until the reaction is finished to obtain a second mixture;
s5, adjusting the pH value of the second mixture obtained in the step S4 by using a 10 wt% -20 wt% sodium hydroxide aqueous solution, washing by using 0.02 wt% -0.04 wt% ethylene diamine tetraacetic acid aqueous solution and deionized water in sequence, and drying to obtain poly (p-phenylene terephthalamide);
s6, dissolving the poly-p-phenylene terephthalamide obtained in the step S5 in tetrahydrofuran, and uniformly mixing at the temperature of 40-60 ℃ to prepare 10-15 wt% of spinning solution;
s7, the spinning solution obtained in the step S6 is filled into an electrostatic spinning device, and is sprayed to form the para-aramid fiber under the action of a 50kV-80kV direct-current high-voltage electric field.
In the embodiment of the invention, the chlorine-containing monomer and the ammonia-containing monomer are introduced, so that the occurrence of phase change is avoided, molecules cannot be closely arranged, the free volume is increased, and the hydrogen bond effect among the molecules is weakened, so that the crystallinity of the polymer is reduced, and the solubility is improved. The para-aramid fiber is obtained by spraying through an injection or spraying device in an electrostatic spinning device, so that monomer raw materials containing benzenesulfonic acid groups are adopted to participate in polymerization reaction, and after the polymerization reaction is finished, positive and negative ions are grafted on a molecular chain of the poly (p-phenylene terephthalamide) with the sulfonic acid groups, so that the fluidity of the polymer is improved, and the smooth operation of the injection or spraying process is ensured. Therefore, the poly (p-phenylene terephthalamide) of the embodiment of the invention not only has excellent self-flowing performance, but also is more suitable for electrostatic spinning.
In addition, compared with the poly-p-phenylene terephthalamide only dissolved in concentrated sulfuric acid in the prior art, the poly-p-phenylene terephthalamide obtained by polymerizing the monomer raw materials according to the embodiment of the invention can be dissolved in tetrahydrofuran. The strong corrosiveness of the sulfuric acid can cause adverse effects on equipment, and the spinning solution taking the sulfuric acid as a solvent is difficult to modify by adding other organic or inorganic materials. According to the invention, by preparing the poly-p-phenylene terephthalamide capable of being dissolved in tetrahydrofuran, inorganic or organic fillers can be added into the poly-p-phenylene terephthalamide spinning solution before the electrostatic spinning process, and particularly, the porosity and the conductivity of the para-aramid can be increased by adding the fillers with porous forms.
In the embodiment of the invention, as the solubility of the polymerization product in the solvent is continuously reduced along with the continuous progress of the polymerization reaction, in order to ensure the continuous progress of the reaction and the viscosity of the polymerization product, anhydrous lithium chloride is added into a polar solvent prepared from N, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone as an auxiliary additive, the continuous progress of the reaction is ensured through the complexation between the lithium chloride and the polar solvent, and the complexation product between the lithium chloride and the N-methylpyrrolidone can further react with the amino hydrogen on the molecular chain of the polymerization product, so that the hydrogen bonds among the molecular chains are further weakened, and the molecular weight of the polymer is improved.
After obtaining a polymerization product, the embodiment of the invention adjusts the pH value by adopting 10 wt% -20 wt% of sodium hydroxide aqueous solution, and repeatedly washes by adopting 0.02 wt% -0.04 wt% of ethylenediamine tetraacetic acid aqueous solution and deionized water for many times. Wherein, the sodium hydroxide aqueous solution can neutralize the micromolecule hydrochloric acid which is continuously generated in the reaction. Because lithium chloride is adopted as an auxiliary additive of the polar solvent in the embodiment of the invention, lithium ions adsorbed on the surface of the polymer are difficult to be completely conscious and removed after the reaction is finished. The residual lithium ions can react with a solvent of a spinning solution in a subsequent electrostatic spinning process to form impurities in the para-aramid fiber, so that the performance of the para-aramid fiber is influenced, and especially the electrochemical stability of the product is reduced. Therefore, in order to completely remove the residual lithium ions, in the embodiment of the invention, the polymerization product is cleaned by using 0.02 wt% -0.04 wt% of the ethylenediaminetetraacetic acid aqueous solution, so that the lithium ions adsorbed on the surface of the polymer are complexed with the ethylenediaminetetraacetic acid, and the complex product of the lithium ions and the ethylenediaminetetraacetic acid can be easily cleaned by water, so that the pH value is adjusted by using the sodium hydroxide aqueous solution, and the polymerization product is repeatedly washed by using the ethylenediaminetetraacetic acid aqueous solution and the deionized water for many times, so that the electrochemical stability of the para-aramid fiber can be improved, and the para-aramid fiber is particularly suitable for manufacturing a lithium battery diaphragm.
In the embodiment of the invention, poly-p-phenylene terephthalamide obtained by polymerization is dissolved in an organic solvent to prepare a spinning solution, and the spinning solution is sprayed by an electrostatic spinning device to form the para-aramid fiber. Electrostatic spinning is a process of forming fibers from polymer solution or polymer melt under the action of a high-voltage electrostatic field, and the main principle is that charged polymer solution or melt flows, splits and deforms in the electrostatic field, and then is solidified through solvent evaporation or melt cooling, and finally a fiber film is obtained. The diameter of the fibers prepared by the electrospinning technology can be between hundreds of nanometers and micrometers. The electrostatic spinning technology is suitable for the preparation in the membrane direction due to the characteristics of simple spinning equipment, short operation time, small using amount of spinning solution and the like. The prepared membrane has the excellent characteristics of large specific surface area, high porosity, small pore diameter and the like. Therefore, compared with the traditional para-aramid fiber spinning process such as dry jet wet spinning, the electrostatic spinning is more suitable for preparing the para-aramid fiber lithium battery diaphragm.
Specifically, as shown in fig. 1, the electrospinning device includes an injector 1, a propeller 2 and a capillary tube 3 respectively located at two ends of the injector 1, a receiving device 4 grounded at the front end of the capillary tube 3 is provided, and a high-voltage electric field is applied between the capillary tube 3 and the receiving device 4 through a high-voltage electricity generating device 5. The spinning solution obtained in step S6 is loaded into the syringe 1, and the spinning solution is ejected from the capillary needle tube 3 toward the receiving device 4 as a jet stream by the propulsion of the propeller 2, and the jet stream is solidified to form a para-aramid fiber as the solvent is volatilized, and is collected by the receiving device 4. Wherein, the propelling speed parameter of the injector 1 is 0.2ml/h-2ml/h, the needle head is No. 7, the receiving device 4 is a roller, the rotating speed of the roller is 12m/min-14m/min, the length of the roller is 280mm, the diameter is 50mm, and the distance between the capillary needle tube 3 and the receiving device 4 is 10cm-12 cm. The embodiment of the invention can obtain the para-aramid fiber which is in disordered arrangement and is particularly suitable for preparing the lithium battery diaphragm through electrostatic spinning.
In order to improve the porosity, mechanical strength and ionic conductivity of the para-aramid fiber of the embodiment of the present invention, in some embodiments of the present invention, an amount of an inorganic microporous filler may be added to the poly (p-phenylene terephthalamide) obtained through step S5, and in particular, the preparation method of the para-aramid fiber of the embodiment of the present invention includes the following steps:
s1, preparing p-phenylenediamine: o-chloro-p-phenylenediamine: 3,4' -diaminodiphenyl ether: 2, 5-diaminobenzenesulfonic acid: terephthaloyl chloride ═ (10-20): (10-20): (5-10): (5-10): (50-60) weighing monomer raw materials in a molar ratio;
s2, according to the weight ratio of N, N-dimethylformamide: n, N-dimethylacetamide: n-methylpyrrolidone ═ (20-30): (20-30): (40-60), weighing the solvent raw materials according to the volume ratio, uniformly mixing, and adding anhydrous lithium chloride: solvent raw materials (2-2.5): 100, adding anhydrous lithium chloride into the solvent raw material, heating to 80-100 ℃, and uniformly mixing again to obtain a polar solvent;
s3, adding the p-phenylenediamine, the o-chloro-p-phenylenediamine, the 3,4' -diaminodiphenyl ether and the 2, 5-diaminobenzenesulfonic acid weighed in the step S1 into a reaction kettle, pumping the polar solvent prepared in the step S2 into the reaction kettle, heating the mixture to 10-30 ℃ under the protection of nitrogen, and stirring the mixture until the mixture is completely dissolved to obtain a first mixture with the molar concentration of 0.4-0.5 mol/L;
s4, under the protection of nitrogen, cooling the first mixture obtained in the step S3 to-5 ℃ within 30min, adding the terephthaloyl chloride weighed in the step S1, and stirring for 10-30min until the reaction is finished to obtain a second mixture;
s5, adjusting the pH value of the second mixture obtained in the step S4 by using a 10 wt% -20 wt% sodium hydroxide aqueous solution, washing by using 0.02 wt% -0.04 wt% ethylene diamine tetraacetic acid aqueous solution and deionized water in sequence, and drying to obtain poly (p-phenylene terephthalamide);
s6, dissolving the poly-p-phenylene terephthalamide obtained in the step S5 in tetrahydrofuran, uniformly mixing at the temperature of 40-60 ℃, preparing 10-15 wt% of spinning solution, adding an inorganic microporous filler into the spinning solution, and uniformly mixing again;
s7, the spinning solution obtained in the step S6 is filled into an electrostatic spinning device, and is sprayed to form the para-aramid fiber under the action of a 50kV-80kV direct-current high-voltage electric field.
The step S6 specifically includes the following sub-steps:
s6-1, dissolving the poly-p-phenylene terephthalamide obtained in the step S5 in tetrahydrofuran, and uniformly mixing at the temperature of 40-60 ℃ to prepare 10-15 wt% of spinning solution;
s6-2, preparing vinylidene fluoride-hexafluoropropylene: weighing raw materials according to the mass ratio of 1:2, stirring the raw materials at the temperature of 60-70 ℃ until the raw materials are completely dissolved, and preparing an organic solution;
s6-3, adding 5-10 wt% of inorganic microporous filler and 0.1-0.2 wt% of sodium hexametaphosphate into the organic solution, and ultrasonically stirring uniformly to obtain an inorganic-organic composite solution;
s6-4. the spinning solution obtained by the step S6-1 and the inorganic-organic composite solution obtained by the step S6-3 were mixed as follows (4-6): 1, and obtaining the spinning solution mixed with the inorganic microporous filler.
Wherein, the inorganic microporous filler used in the step S6-3 is prepared by the following method:
A1. according to the weight percentage of hydroxyapatite: zirconium oxide: germanium oxide: tellurium oxide: weighing raw materials (4-6) - (6-8) - (20-30) - (30-40) by mass, adding sodium alginate accounting for 2-4% of the total mass of the raw materials into the raw materials, grinding and uniformly mixing to obtain an inorganic powder composition;
A2. calcining the inorganic powder composition obtained in the step A1 at the temperature of 600-800 ℃ for 60-120 min, and cooling to room temperature along with the furnace;
A3. the calcined inorganic powder composition obtained by step a2 is washed, filtered, and dried.
Through the steps, the loose inorganic microporous filler with small particle size, uniform particle size distribution and high porosity can be obtained. Compared with the method that inorganic powder such as silicon oxide, zirconium oxide and the like is directly mixed with organic solution, the porous microsphere structure can be formed by adding hydroxyapatite and sodium alginate into the silicon oxide and zirconium oxide powder and calcining the mixture, the melting point and the calcining temperature of the powder can be reduced by adding germanium oxide and tellurium oxide, and the porous microsphere structure is prevented from being damaged by high temperature. Therefore, the inorganic microporous filler prepared by the steps A1 to A3 and the poly-p-phenylene terephthamide are used together to prepare the spinning solution and are subjected to electrostatic spinning, so that the para-aramid fiber with excellent porosity, mechanical strength and ionic conductivity can be obtained.
It will be appreciated by those skilled in the art that changes and modifications may be made to the specific embodiments described above without departing from the inventive concept, and that various combinations of features and structures may be practiced without departing from the scope of the invention as defined in the appended claims.
Claims (2)
1. A preparation method of para-aramid fiber is characterized by comprising the following steps: p-phenylenediamine, o-chloro-p-phenylenediamine, 3,4' -diaminodiphenyl ether, 2, 5-diaminobenzene sulfonic acid and terephthaloyl chloride are used as monomer raw materials, a mixture of N, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone is used as a polar solvent, poly-p-phenylene terephthalamide is prepared through low-temperature solution polycondensation, and the poly-p-phenylene terephthalamide is used for electrostatic spinning to prepare para-aramid fibers;
the preparation method of the para-aramid fiber specifically comprises the following steps:
s1, preparing p-phenylenediamine: o-chloro-p-phenylenediamine: 3,4' -diaminodiphenyl ether: 2, 5-diaminobenzenesulfonic acid: terephthaloyl chloride ═ (10-20): (10-20): (5-10): (5-10): (50-60) weighing monomer raw materials in a molar ratio;
s2, according to the weight ratio of N, N-dimethylformamide: n, N-dimethylacetamide: n-methylpyrrolidone ═ (20-30): (20-30): (40-60), weighing the solvent raw materials according to the volume ratio, uniformly mixing, and adding anhydrous lithium chloride: solvent raw materials (2-2.5): 100, adding anhydrous lithium chloride into the solvent raw material, heating to 80-100 ℃, and uniformly mixing again to obtain a polar solvent;
s3, adding the p-phenylenediamine, the o-chloro-p-phenylenediamine, the 3,4' -diaminodiphenyl ether and the 2, 5-diaminobenzenesulfonic acid weighed in the step S1 into a reaction kettle, pumping the polar solvent prepared in the step S2 into the reaction kettle, heating the mixture to 10-30 ℃ under the protection of nitrogen, and stirring the mixture until the mixture is completely dissolved to obtain a first mixture with the molar concentration of 0.4-0.5 mol/L;
s4, under the protection of nitrogen, cooling the first mixture obtained in the step S3 to-5 ℃ within 30min, adding the terephthaloyl chloride weighed in the step S1, and stirring for 10-30min until the reaction is finished to obtain a second mixture;
s5, sequentially adopting 10-20 wt% of sodium hydroxide aqueous solution to adjust the pH of the second mixture obtained in the step S4, sequentially adopting 0.02-0.04 wt% of ethylene diamine tetraacetic acid aqueous solution and deionized water to wash and dry the mixture to obtain poly-p-phenylene terephthalamide;
s6, dissolving the poly-p-phenylene terephthalamide obtained in the step S5 in tetrahydrofuran, and uniformly mixing at the temperature of 40-60 ℃ to prepare 10-15 wt% of spinning solution;
s7, loading the spinning solution obtained in the step S6 into an electrostatic spinning device, and spraying the spinning solution to form para-aramid fibers under the action of a 50kV-80kV direct-current high-voltage electric field;
step S6 specifically includes the following substeps:
s6-1, dissolving the poly-p-phenylene terephthalamide obtained in the step S5 in tetrahydrofuran, and uniformly mixing at the temperature of 40-60 ℃ to prepare 10-15 wt% of spinning solution;
s6-2, preparing vinylidene fluoride-hexafluoropropylene: weighing raw materials according to the mass ratio of 1:2, stirring the raw materials at the temperature of 60-70 ℃ until the raw materials are completely dissolved, and preparing an organic solution;
s6-3, adding 5-10 wt% of inorganic microporous filler and 0.1-0.2 wt% of sodium hexametaphosphate into the organic solution, and ultrasonically stirring uniformly to obtain an inorganic-organic composite solution;
s6-4. the spinning solution obtained by the step S6-1 and the inorganic-organic composite solution obtained by the step S6-3 were mixed as follows (4-6): 1, and uniformly mixing to obtain a spinning solution mixed with the inorganic microporous filler;
wherein, the inorganic microporous filler used in the step S6-3 is prepared by the following method:
A1. according to the weight percentage of hydroxyapatite: zirconium oxide: germanium oxide: tellurium oxide: weighing raw materials (4-6) - (6-8) - (20-30) - (30-40) by mass, adding sodium alginate accounting for 2-4% of the total mass of the raw materials into the raw materials, grinding and uniformly mixing to obtain an inorganic powder composition;
A2. calcining the inorganic powder composition obtained in the step A1 at the temperature of 600-800 ℃ for 60-120 min, and cooling to room temperature along with the furnace;
A3. the calcined inorganic powder composition obtained by step a2 is washed, filtered, and dried.
2. A para-aramid fiber is characterized in that: the para-aramid fiber is prepared by the method as claimed in claim 1.
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